Metal-working fluids containing microbiocidal naphthenyl imidazolines

ABSTRACT

THE USE OF 1-AMINOETHYL-2-NAPHTHENYL IMIDAZOLINE, HAVING THE STRUCTURE:   1-(H2N-CH2-CH2-),2-R-2-IMIDAZOLINE   WHEREIN R IS THE RESIDUE OF A NAPHTHENE-CARBOXYLIC ACID, AS A MICROBICIDAL PRESERVATIVE AGENT IN METAL WORKING FLUIDS.

3,827,874 METAL-WORKING FLUIDS CONTAINING MICRO- BIOCIDAL NAPHTHENYLIMIDAZOLINES Phillip Adams, Murray Hill, and Alfonso N. Petrocci,

Glen Rock, N..'l., assignors to Millmaster Onyx Corporation, New York,N.Y.

No Drawing. Continuation-impart of application Ser. No. 883,641, Dec. 9,1969, now Patent No. 3,705,027. This application Oct. 18, 1972, Ser. No.298,758 The portion of the term of the patent subsequent to Dec. 5,1989, has been disclaimed Int. Cl. A0111 9/22 US. CI. 71-67 2 ClaimsABSTRACT OF THE DISCLOSURE The use of 1-aminoethyl-2-naphthenylimidazoline, having the structure:

wherein R is the residue of a naphthene-carboxylic acid, as amicrobiocidal preservative agent in metal working fluids.

This is a continuation-in-part of co-pending application Ser. No.883,641, filed Dec. 9, 1969, and now issued as Pat. No. 3,705,027, datedDec. 5, 1972. This invention relates to the microbiocidal use ofl-aminoethyl-Z-naphthenyl imidazoline, having the structure:

wherein R is the residue of a naphthene-carboxylic acid.

It has been discovered that the above naphthenyl imidazolines have ahigh order of microbiocidal effectiveness which is greatly superior toother imidazolines having different acid residues.

These compounds are especially useful as preservatives for metal-workinglubricants, such as cutting and grinding fluids, against microbialdecomposition which causes breaking of emulsions, putrefaction and theincidence of dermatitis resulting from the handling of contaminated orspoiled lubricants.

Naphthenic acids are well known to the art and are availablecommercially, primarily as the result of various extractive procedurescarried out in refining naturally occurring petroleums and petroleumfractions, particularly gas-oil distillates boiling in the range of400700 F. Naphthenic acids are found particularly in petroleumsoriginating in the western part of the United States, especially inCalifornia; in the northern part of South America, especially Venezuela,Colombia and Aruba; in the southern part of Europe, especially Rumania,and, to a lesser extent, in crude oils originating in Louisiana, alongnited States Patent the Texas gulf coast, in Peru, Mexico, Poland, theSoviet Union and Germany.

The chemical nature of these naphthenic acids is more or lessill-defined, but they all have in common the characteristic ofpossessing alicyclic nuclei. These may be five or six membered carbonatom ring systems, various condensed ring systems, and other relatedmaterials as disclosed in Fieser, Organic Chemistry, 3rd ed., 1956,pages 97-98.

EXAMPLE 1 2,324 grams (or 9.28 mols) of Enjays Refined Naphthenic Acidhaving an acid number of 224, and 1,265 grams (or 12.07 mols) ofdiethylene triamine were charged into an agitated flask fitted with apacked fractionating column system for the purpose of separating andremoving water formed in the reaction and returning stripped amine tothe reactor. Aquametric titration of the charged amine indicated a watercontent of 1.17%

The mixture was agitated and heated under reduced pressure at about C.pot temperature and at 216 mm. pressure, gradually raising the pottemperature to about 200 C. during a period of about 12 hours. The waterof reaction distilled along with some of the diethylene triamine,through the fractionating column, which stripped off the water andreturned the amine to the reactor. When no more water distilled, theexcess amine was distilled oif at about 5 mm. pressure and C.

The total amount of water collected was 321 grams; correcting for theinitial water content, 17 mols of water was obtained, or 91.5% of thetheoretical amount for the formation of the imidazoline.

A weighed sample was titrated potentiometrically to the first break withHCl in alcohol, indicating 87.4% activity. After reacting thenon-tertiary nitrogen with phenyl isothiocyanate, titration withperchloric acid indicated 95.2% reaction.

The product was found to be effective against aerobic bacteria at from25 to 150 parts per million at 37 C. during four hours.

EXAMPLE 2 The product was assayed bacteriologically by the StandardBroth Dilution Test Method. Aliquots of a solution of the aminoethylnaphthenyl imidazoline were added to appropriate broth culture mediacontained in test tubes, so that various concentrations were obtained.The tubes so prepared were inoculated with 24 hours broth cultures ofthe test bacteria, or 14 day aqueous spore suspensions of the testfungi, or 7 day broth cultures of the algae. The inoculated tubes wereincubated as follows: bacteria for 72 hours at 37 C.; fungi for 14 daysat 28 C.; algae for 7 days at 25 C. Following the aforementionedincubation periods, the tubes were examined for the presence or absenceof macroscopic growth. The lowest concentration of test material notpermitting macroscopic growth is des ignated as the Minimum InhibitoryLevel.

The test organisms employed were:

Escherichia coli E.c. Pseudomonas aeruginosa Ps. a. Staphylococcusaureus S.a. Streptococcus faecalis SJ. Aspergillws niger A.n. Peniciliumexpansum P.e.

Chlorella pyrenoidosa C.p.

3 TABLE I Parts per million of l-aminoethyl-Z-naphthenyl imidazolineGram Negative:

These compounds may be employed either as the free amines or as theirsalts of inorganic or organic acids. Such acids may include, forexample, hydrochloric, sulfuric, phosphoric, acetic, lauric, oleic,gluconic, oxalic, tartaric, citric, benzoic and substituted benzoic,paratoluene sulfonic, sulfamic, and the like.

The present compounds are especially useful when introduced intometal-working fluids, to preserve them against microbial action whichresults in decomposition and putrefaction, or breaking of emulsions, orto prevent dermatitis resulting from contact with spoiled cutting andgrinding oils and the like.

Cutting and grinding fluids and especially the watersoluble orwater-dispersible types containing, for example, the amine soaps, andsalts of organic phosphate esters, tallow soaps, mahogany soaps andother hydrocarbon sulfonates, were eifectively preserved againstmicrobial action over a period of weeks by the addition of about 200parts per million of the imidazoline in the lubricant as diluted foruse.

The following examples serve as illustrations of some specificmetal-working fluid formulations containing effective amounts of acomupound embodying the present invention:

EXAMPLE 3 A phosphate ester type metal-working fluid Components: Partsby Weight Antara LS-500 (phosphate ester) 10.0 Triethanolamine 20.0Sodium nitrite 4.0

1-aminoethyl-2-naphthenyl imidazoline 1.0 to 2.0 Water, Q.s. 100.0

4 EXAMPLE 4 A petroleum sulfonate type metal-working fluid I Parts byWeight Components:

Humble Oil Co. Acto 630 (petroleum sulfonate) 33.0 Hume Oil Co. \Acto639 (petroleum sulfonate) 33.0 Mineral spirits (i.e. Humble Oil Co.)

Bayol 32.0 to 33.0 1 aminoethyl-Z-naphthenyl imidazoline 1.0 to 2.0

Concentrations of the preservative may vary widely in accordance withmanufacturers specifications and end use of the products. However, infinal dilution, the end product should preferably contain a minimum of200 ppm. of the preservative relative to the total composition. Thisproportion may be increased as desired.

The invention claimed is:

1. A method of inhibiting the growth of bacteria, fungi and algae inmetal-working cutting and grinding fluids which comprises applying tothe growth in said fluids an amount sufiicient to inhibit such growth ofthe compound 1-aminoethyl-2-naphthenyl imidazoline or a salt thereof.

2. The method of claim 1 wherein said salt is selected from the groupconsisting of the hydrochloric, sulfuric, phosphoric, acetic, lauric,oleic, gluconic, oxalic, tartaric, citric, benzoic, paratoluene sulfonicand sulfamic acid salts.

References Cited UNITED STATES PATENTS 2,738,325 3/1956 Rydell 424-2732,832,715 4/1958 Jezl et al. 4243O 3,251,662 5/1966 Fareri et al. 42A2733,502,578 3/1970 Raifsnider 2l0309.6 3,705,027 12/1972 Adams et al.424-273 JAMES O. THOMAS, 111., Primary Examiner US. Cl. X.R.

